双官能化的环戊二烯基钛/锆络合物的合成及催化乙烯与1-己烯的共聚
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摘要
合成了一系列含有烯丙基和芳基的茂金属络合物,通过核磁共振氢谱(~1H-NMR)、核磁共振碳谱(~(13)C-NMR)、质谱(MS)和元素分析(EA)表征,确认了其化学组成,在甲基铝氧烷(MAO)助催化下,这些茂金属络合物有效催化乙烯聚合以及乙烯与1-己烯共聚,在50℃、1.0 MPa时,催化活性最高达到520 kg/(mol·h)。研究结果表明,烯丙基的引入稳定了催化活性中心,使得聚合反应能够在较高温度下进行,芳基的引入提高了该类络合物的共聚能力。同时还研究了聚合温度、助催化剂比例等因素对聚合反应的影响,结果表明,随着聚合温度升高催化活性先升高后降低,80℃时活性最高,为352 kg/(mol·h);含有双官能团的茂金属催化活性随着助催化剂比例升高而升高,聚合物分子量随着助催化剂比例升高而降低;1-己烯插入率最高可达4.30%,这表明双官能化茂金属有效提高了双配体茂金属共聚能力。
Allyl and aryl groups with weak coordination effect have great influences on the catalytic behavior of metallocene. In order to investigate the catalytic behavior of metallocene in the presence of both allyl and aryl groups,the Group IV metal complexes with allyl and aryl groups on cyclopentadienyl ligands(Cp) were synthesized and characterized with ~1 H-NMR, ~(13) C-NMR, MS and EA. When combined with methylaluminoxane(MAO), the bifunctional metallocene complexes indicated relativelyhigh catalytic activity for ethylene polymerization and ethylene copolymerization with 1-hexene. When T = 50 ℃, p = 1.0 MPa, the catalytic activity for ethylene polyerization reaches520 kg/(mol·h). The polymerization results showed that the steric effect of substituent group on Cp ring has great influence on the behavior of catalyst, while the(BifunctionalCp)_2 MCl_2 displayed very low activity. However, the mixed CpMCl_2 showed moderate activity under same condition. It is worth to note that compared to mono functional group,the introduction of both allyl and aryl groups not only enhances the copolymerization ability(inserting yield of 1-hexene reaches 4.30%), but also makes the catalyst keeping moderate activity at higher polymerization temperature(Activity reached 156 kg/(mol·h) at 100 °C), which is called as bifunctional effect. The effects of polymerization reaction factors such as temperature, mole ratio of Al/metal and the concentration of catalyst on polymerization reaction have been investigated. It is found that upon incrasing temperature the catalytic activity increased first and then decreased. The activity reached 352 kg/(mol·h) when polymerization temperature is 80 ℃. In fact, the catalytic activity of bifunctional metallocene increased continually as the ratio of n Al/n Ti increased, but the polymer molecular weight decreased continually at the same time. However, the catalytic activity decreased as the concentration of catalyst increased,while the polymer's molecular weight increased first and then decreased.
Allyl and aryl groups with weak coordination effect have great influences on the catalytic behavior of metallocene. In order to investigate the catalytic behavior of metallocene in the presence of both allyl and aryl groups,the Group IV metal complexes with allyl and aryl groups on cyclopentadienyl ligands(Cp) were synthesized and characterized with ~1 H-NMR, ~(13) C-NMR, MS and EA. When combined with methylaluminoxane(MAO), the bifunctional metallocene complexes indicated relativelyhigh catalytic activity for ethylene polymerization and ethylene copolymerization with 1-hexene. When T = 50 ℃, p = 1.0 MPa, the catalytic activity for ethylene polyerization reaches520 kg/(mol·h). The polymerization results showed that the steric effect of substituent group on Cp ring has great influence on the behavior of catalyst, while the(BifunctionalCp)_2 MCl_2 displayed very low activity. However, the mixed CpMCl_2 showed moderate activity under same condition. It is worth to note that compared to mono functional group,the introduction of both allyl and aryl groups not only enhances the copolymerization ability(inserting yield of 1-hexene reaches 4.30%), but also makes the catalyst keeping moderate activity at higher polymerization temperature(Activity reached 156 kg/(mol·h) at 100 °C), which is called as bifunctional effect. The effects of polymerization reaction factors such as temperature, mole ratio of Al/metal and the concentration of catalyst on polymerization reaction have been investigated. It is found that upon incrasing temperature the catalytic activity increased first and then decreased. The activity reached 352 kg/(mol·h) when polymerization temperature is 80 ℃. In fact, the catalytic activity of bifunctional metallocene increased continually as the ratio of n Al/n Ti increased, but the polymer molecular weight decreased continually at the same time. However, the catalytic activity decreased as the concentration of catalyst increased,while the polymer's molecular weight increased first and then decreased.
引文
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[28]WANG F,FANG M,WU W,et al.Mass spectrometry of derivatives of dicyclopentadienyltitanium dichloride:II.Comparison of chemical ionization and liquid secondary ion mass spectrometric behavior[J].Rapid Communications in Mass Spectrometry,1995,9(14):1362-1365.
[29]LICHT E H,ALT H G,KARINA M M.ω-Phenylalkyl-substituted zirconocene dichloride complexes as catalyst precursors for homogeneous ethylene polymerization[J].Journal of Organometallic Chemistry,2000,599(2):275-287.
[30]许胜,黄吉玲.大取代茂锆配合物合成及分子内消除反应研究[J].化学学报,2005,63(14):1318-1322.
[2]DELFERRO M,MARKS T.Multinuclear olefin polymerization catalysts[J].Chemical Reviews,2011,111:2450-2485.
[3]马越,程瑞华,何雪莲,等.钛改性硅胶负载Cr-Mo复合乙烯聚合Phillips催化剂[J].华东理工大学学报(自然科学版),2016,42(2):163-170,253.
[4]WANNABORWORN M,PRASERTHDAM P,JONG-SOMJIT B.Observation of different catalytic activity of various 1-olefins during Ethylene/1-Olefin copolymerization with homogeneous metallocene catalysts[J].Molecules,2011,16(1):373-383.
[5]MORTON J G M,HAIF A S,SUN Y S,et al.1,1-Olefinbridged bis-(2-indenyl)metallocenes of titanium and zirconium[J].Dalton Transactions,2014,43(35):13219-13231.
[6]许胜,梁春超,吕中文,等.双核茂钛催化剂中苄基苯环的弱作用效应对乙烯聚合行为影响的研究[J].有机化学,2017,37(5):1284-1289.
[7]MCINNIS J P,DELFERRO M,MARKS T J.Multinuclear group 4 catalysis:Olefin polymerization pathways modified by strong metal-metal cooperative effects[J].Accounts of Chemical Research,2014,47(8):2545-2557.
[8]LIU S F,INVERGO A M,MCINNIS J P,et al.Distinctive stereochemically linked cooperative effects in bimetallic titanium olefin polymerization catalysts[J].Organometallics,2017,36(22):4403-4421.
[9]MI P K,KONG X J,XU S,et al.Synthesis of sp3 C1-bridged constrained geometry complexes and their application for copolymerization of ethylene and 1-octene[J].Advanced Materials Research,2013,683:280-288.
[10]TANG X Y,LONG Y Y,WANG Y X,et al.Synthesis and characterization of phosphine-(thio)phenolatebased half-zirconocenes and their application in ethylene(co-)polymerization[J].Dalton Transactions,2014,43:222-230.
[11]YAO C G,WU C J,WANG B L,et al.Copolymerization of ethylene with 1-hexene and 1-octene catalyzed by fluorenyl N-heterocyclic carbene ligated rare-earth metal precursors[J].Organometallics,2013,32:2204-2209.
[12]NOMURA K,FUKUDA H,MATSUDA H,et al.Synthesis and structural analysis of half-titanocenes containing 1,3-imidazolidin-2-iminato ligands:Effect of ligand substituents in ethylene(co)polymerization Srisuda Patamma[J].Journal of Organometallic Chemistry,2015,798:375-383.
[13]APISUK W,KITIYANAN B,KIM H J,et al.Introduction of reactive functionality by the incorporation of divinylbiphenyl in ethylene copolymerization with styrene or 1-hexene using aryloxo-modified half-titanocenes and mao catalysts[J].Journal of Polumer Science:Part A.Polymer Chemistry,2013,51(12):2581-2587.
[14]DONG B,ZHANG H X,LI H,et al.Half-titanocene complexes bearing bulky dibenzhydryl-substituted aryloxide ligand:Syntheses,characterization,and ethylene(Co-)polymerization behaviors[J].Polymer,2016,100(9):188-193.
[15]ZHANG W J,HUANG W,LIANG T L,et al.Half-titanocene chlorides 2-(benzimidazol-2-yl)quinolin-8-olates:Synthesis,sharacterization and ethylene co-polymerization behavior[J].Chinese Journal of Polymer Science,2013,31(4):601-609.
[16]YAN Q,YANG W H,CHEN L Q,et al.Half-titanocene 5-t-butyl-2-(1-(arylimino)methyl)quinolin-8-olate chlorides:Synthesis,characterization and ethylene(co-)polymerization behavior[J].Journal of Organometallic Chemistry,2014,753:34-41.
[17]ZHANG Q,TAO X,GAO W,et al.Pentamethylcyclopentadienyltitanium aryl(pyridyl)amide complexes:Synthesis,characterization and catalytic performance for olefin polymerization[J].Journal of Organometallic Chemistry,2016,804:18-25.
[18]LIU K F,WU Q L,GAO W,et al.Half-zirconocene anilide complexes:Synthesis,characterization and catalytic properties for ethylene polymerization and copolymerization with1-hexene[J].Dalton Transactions,2011,40(17):4715-4721.
[19]HUANG W Z,SUN X Q,MA H Y,et al.Ethylene homopolymerization and ethylene/1-hexene copolymerization catalyzed by mixed salicylaldiminato cyclopentadienyl zirconium complexes[J].Inorganica Chimica Acta,2010,363(9):2009-2015.
[20]BERGAMO A L,CHAGAS R P,CASAGRANDE O L J.Half-metallocene zirconium complex bearing tridentate[N,N,O]ligand and its use in homo-and copolymerization of ethylene,Half-metallocene zirconium complex bearing tridentate[N,N,O]ligand and its use in homo-and copolymerization of ethylene[J].Catalysis Communications,2013,42(23):113-115.
[21]QIAN Y L,HUANG J L,BALA M D,et al.Synthesis,structures,and catalytic reactions of ring-substituted titanium(IV)complexes[J].Chemical Review,2003,103(7):2633-90.
[22]PEREZ O,JOAO B P,MARICELA G,et al.Copolymerization of ethylene/α-olefins using bis(2-phenylindenyl)zirconium dichloride metallocene catalyst:Structural study of comonomer distribution[J].Polymer International,2010,59(9):1258-1265.
[23]XU S,JIA J J,HUANG J J.Synthesis of double silylenebridged binuclear zrconium complexes and their use as catalysts for o;efin polymerization[J].Journal Polymer Science:Part A.Polymer Chemistry,2007,45(21):4901-4913.
[24]SIERRA J C,HUEERLAENDER D,HILL M,et al.Formation of dinuclear titanium and zirconium complexes by olefin metathesis-catalytic preparation of organometallic catalyst systems[J].Chemistry,2003,9(15):3618-3622.
[25]KUWABARA J,TAKEUCHI D,OSAKADA K.Zr/Zr and Zr/Fe dinuclear complexes with flexible bridging ligands preparation by olefin metathesis reaction of the mononuclear precursors and properties as polymerization catalysts[J].Organometallics,2005,24(11):2705-2712.
[26]STONE K J,LITTLE R D.An exceptionally simple and efficient method for the preparation of a wide variety of fulvenes[J].Journal Organic Chemistry,1984,49(11):2-6.
[27]TUMAY T A,KEHR G,FROHLICH R,et al.Ring-closing metathesis of sterically congested functionalized zirconocenes-ethene polymerization catalysts derived from related bridged and open metallocenes[J].Dalton Transactions,2009,41(41):8923-8928.
[28]WANG F,FANG M,WU W,et al.Mass spectrometry of derivatives of dicyclopentadienyltitanium dichloride:II.Comparison of chemical ionization and liquid secondary ion mass spectrometric behavior[J].Rapid Communications in Mass Spectrometry,1995,9(14):1362-1365.
[29]LICHT E H,ALT H G,KARINA M M.ω-Phenylalkyl-substituted zirconocene dichloride complexes as catalyst precursors for homogeneous ethylene polymerization[J].Journal of Organometallic Chemistry,2000,599(2):275-287.
[30]许胜,黄吉玲.大取代茂锆配合物合成及分子内消除反应研究[J].化学学报,2005,63(14):1318-1322.